Dimethyl Sulfide → 3-[1-[2-(4-Chlorophenyl)ethyl]-3-oxo-3-phenylpropyl]benzoic acid, methyl ester

HRID 1647230Notes

Reaction equation

HRID 1647230 reaction equation
CN(C)P(N(C)C)(N(C)C)=O.[Cl:12][C:13]1[CH:18]=[CH:17][C:16]([CH2:19][CH2:20]I)=[CH:15][CH:14]=1.CSC.[O:25]=[C:26]([C:39]1[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=1)[CH:27]=[CH:28][C:29]1[CH:30]=[C:31]([CH:36]=[CH:37][CH:38]=1)[C:32]([O:34][CH3:35])=[O:33].C[Si](Cl)(C)C>O1CCCC1.C(OCC)C>[Cl:12][C:13]1[CH:18]=[CH:17][C:16]([CH2:19][CH2:20][CH:28]([C:29]2[CH:30]=[C:31]([CH:36]=[CH:37][CH:38]=2)[C:32]([O:34][CH3:35])=[O:33])[CH2:27][C:26](=[O:25])[C:39]2[CH:40]=[CH:41][CH:42]=[CH:43][CH:44]=2)=[CH:15][CH:14]=1

Participants

8

Reactant 5

HCID 1068Dimethyl SulfideHCID 6397ChlorotrimethylsilaneHCID 12679HexamethylphosphoramideHCID 223147194-Chlorophenethyl iodideHCID 860607263-(3-Oxo-3-phenyl-1-propenyl)-benzoic acid, methyl ester

Product 1

HCID 867487633-[1-[2-(4-Chlorophenyl)ethyl]-3-oxo-3-phenylpropyl]benzoic acid, methyl ester

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-78 °C

Procedure

A solution of SmI2 (48 mL, 0.1N, 4.4 mmol) in tetrahydrofuran is treated with hexamethylphosphoramide (HMPA) (3.75 mL, 2.19 mmol) and stirred 5 minutes. A solution of 1-chloro-4- (2-iodoethyl) -benzene (0.6 g, 2.25 mmol) in tetrahydrofuran (5 mL) is added, stirred 10 minutes and cooled to -78° C. A catalytic amount of CuBr.DMS (45 rag, 0.225 mmol) is added to the reaction mixture which is stirred 5 minutes before a solution of 3-(3-oxo-3-phenyl-1-propenyl)-benzoic acid, methyl ester (0.4 g, 1.5 mmol) and trimethylsilyl chloride (0.75 mL, 5.58 mmol) in tetrahydrofuran (6 mL) is added. The reaction is stirred in the cold for 30 minutes, diluted with diethyl ether (400 mL), and filtered over a 2" cake of Al2O3. The ethereal solution is washed with water, dried (MgSO4), and stirred with a few drops of tetrabutylammonium fluoride for 2 hours. The reaction mixture is concentrated and columned over SiO2 eluting with dichloromethane to collect 0.5 g of an oil which is clean by PMR.

Workup

  1. stirringstirred 10 minutes
  2. additionis added
  3. stirringThe reaction is stirred in the cold for 30 minutes
  4. filtrationfiltered over a 2" cake of Al2O3
  5. washThe ethereal solution is washed with water
  6. dry with materialdried (MgSO4)
  7. stirringstirred with a few drops of tetrabutylammonium fluoride for 2 hours
  8. concentrationThe reaction mixture is concentrated
  9. customto collect 0.5 g of an oil which

Sources & evidence

ORD record
ord-8ac5bf8d3d8347a88474ec815dceb9d8
Source dataset
uspto-grants-1995_07
Patent number
US05430047

Reaction notes

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